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Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations

  • Muhammad H. Esmaiel , Hany A. Basuony , Mohamed K. Al-Nawasany , Musab M. Shulkamy , Ibrahim A. Shaaban , Ahmed M. Abuelela , Wajdi M. Zoghaib and Tarek A. Mohamed EMAIL logo
Published/Copyright: June 22, 2019
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 234 Issue 3

Abstract

Raman (3700–100 cm−1) and infrared (4000–400 cm−1) spectra of 2,5-Dimercapto-1,3,4-thiadiazol (DMTD) were recorded in the solid phase. Six structures (1–6) were initially proposed for DMTD as a result of thiol-thione tautomerism and internal rotation(s) of thiol group(s) around the C–S bond. Quantum chemical calculations were carried out for an isolated molecule (1–6) using density functional theory (B3LYP) and ab initio MP2(full) methods utilizing 6-31G(d) and 6-311++G(d,p) basis sets which favor thiol-thione tautomerism (structure 4). Relaxed potential energy surface scans of structure 4 revealed an additional conformer (the thiol group is out-of-plane, structure 7) using the aforementioned methods at 6-311++G(d,p) basis set. For additional verification, plane-wave solid state calculations were carried out at PW91 and PBEsol came out in favor of conformer 7. This is in agreement with the computed/observed SH in-plane bending of S-7 (959/941 cm−1) rather than the one estimated at (880 cm−1) for S-4. Moreover, the observed split IR/Raman bands were found consistent with solid state calculated frequencies of S-7 assuming two molecules per unit cell bonded via H-bonding intermolecular interactions. Aided by vibrational frequency calculations, normal coordinate analysis, force constants and potential energy distributions (PEDs), a complete vibrational assignment for the observed IR and Raman bands is proposed herein. Furthermore, we have estimated the frontier molecular orbitals and atomic charges to account for the corrosion inhibition efficiency of DMTD along with its binding sites to the metal surface. Our results are discussed herein and compared to similar molecules whenever appropriate.

Keywords: 2,5-Dimercapto-1,3,4-thiadiazol (DMTD); tautomerism; Raman and infrared spectra; vibrational assignment and MP2 = full/DFT calculations

Acknowledgement

TAM sincerely thanks Professor James R. Durig, Chemistry Department, College of Arts and Sciences, University of Missouri, Kansas City, MO 64110, USA, for giving him the opportunity to use G- and F-matrix programs to calculate FCs in internal coordinates and PEDs.

References

1. N. Vasimalai, S. A. John, Analyst 137 (2012) 3349.10.1039/c2an35190kSearch in Google Scholar PubMed

2. X. He, Z. Su, Q. Xie, C. Chen, Y. Fu, L. Chen, Y. Liu, M. Ma, L. Deng, D. Qin, Y. Luo, S. Yao, Microchim. Acta 173 (2011) 95.10.1007/s00604-010-0541-8Search in Google Scholar

3. M. J. Ahmed, I. Jahan, S. Banoo, Anal. Sci. 18 (2002) 805.10.2116/analsci.18.805Search in Google Scholar PubMed

4. Y. Fu, P. Li, L. Bu, T. Wang, Q. Xie, J. Chen, S. Yao, Anal. Chem. 83 (2011) 6511.10.1021/ac200471vSearch in Google Scholar PubMed

5. Y. Fu, C. Zou, Q. Xie, X. Xu, C. Chen, W. Deng, S. Yao, J. Phys. Chem. B 113 (2009) 1332.10.1021/jp807337fSearch in Google Scholar PubMed

6. Ł. Popiołek, U. Kosikowska, M. Dobosz, A. Malm, Phosphorus Sulfur Silicon Relat. Elem. 187 (2012) 468.10.1080/10426507.2011.625511Search in Google Scholar

7. N. S. Jumat Salimon, E. Yousif, A. Hameed, H. Ibraheem, Aust. J. Basic Appl. Sci. 4 (2010/7) 6.Search in Google Scholar

8. N. Rezki, A. Al-Yahyawi, S. Bardaweel, F. Al-Blewi, M. Aouad, Molecules 20 (2015) 16048.10.3390/molecules200916048Search in Google Scholar PubMed PubMed Central

9. A. L. Squissato, W. P. Silva, A. T. S. Del Claro, D. P. Rocha, R. M. Dornellas, E. M. Richter, C. W. Foster, C. E. Banks, R. A. A. Munoz, Talanta 174 (2017) 420.10.1016/j.talanta.2017.06.042Search in Google Scholar PubMed

10. T. T. Qin, J. Li, H. Q. Luo, M. Li, N. B. Li, Corros. Sci. 53 (2011) 1072.10.1016/j.corsci.2010.12.002Search in Google Scholar

11. W. Chen, H. Q. Luo, N. B. Li, Corros. Sci. 53 (2011) 3356.10.1016/j.corsci.2011.06.013Search in Google Scholar

12. X. Yang, Y. Huang, G. Liu, J. Liu, L. Ma, X. Niu, X. Qu, J. Taiwan Inst. Chem. E. 93 (2018) 109.10.1016/j.jtice.2018.09.022Search in Google Scholar

13. Y. El Bakri, L. Guo, E. H. Anouar, E. M. Essassi, J. Mol. Liq. 274 (2019) 759.10.1016/j.molliq.2018.11.048Search in Google Scholar

14. N. Vasimalai, G. Sheeba, S. A. John, J. Hazard Mater 213–214 (2012) 193.10.1016/j.jhazmat.2012.01.079Search in Google Scholar

15. P. Kannan, S. A. John, Anal. Biochem. 386 (2009) 65.10.1016/j.ab.2008.11.043Search in Google Scholar

16. L. Jin, G. Wang, X. Li, L. Li, J. Appl. Electrochem. 41 (2011) 377.10.1007/s10800-010-0246-zSearch in Google Scholar

17. Y. Kiya, G. R. Hutchison, J. C. Henderson, T. Sarukawa, O. Hatozaki, N. Oyama, H. D. Abruña, Langmuir 22 (2006) 10554.10.1021/la061213qSearch in Google Scholar

18. J. Gao, M. A. Lowe, S. Conte, S. E. Burkhardt, H. D. Abruña, Chem. Eur. J. 18 (2012) 8521.10.1002/chem.201103535Search in Google Scholar

19. H. G. M. Edwards, A. F. Johnson, E. E. Lawson, J. Mol. Struct. 351 (1995) 51.10.1016/0022-2860(94)08485-ZSearch in Google Scholar

20. J. M. Pope, T. Sato, E. Shoji, D. A. Buttry, T. Sotomura, N. Oyama, J. Power Sources 68 (1997) 739.10.1016/S0378-7753(96)02598-0Search in Google Scholar

21. E. E. Lawson, H. G. M. Edwards, A. F. Johnson, J. Raman Spectrosc 26 (1995) 617.10.1002/jrs.1250260806Search in Google Scholar

22. F. Hipler, R. A. Fischer, J. Müller, J. Chem. Soc. Perkin Trans. 2 (2002) 1620.10.1039/B201887JSearch in Google Scholar

23. S. Millefiori, A. Millefiori, J. Mol. Struct. Theochem 151 (1987) 373.10.1016/0166-1280(87)85072-8Search in Google Scholar

24. K. L. Williamson, J. D. Roberts, Heterocycles 11 (1978) 12.10.3987/S(N)-1978-01-0121Search in Google Scholar

25. A. R. Katritzky, Z. Wang, R. J. Offerman, J. Heterocycl. Chem. 27 (1990) 139.10.1002/jhet.5570270204Search in Google Scholar

26. N. Maiti, R. Chadha, A. Das, S. Kapoor, RSC Adv. 6 (2016) 62529.10.1039/C6RA10404ESearch in Google Scholar

27. J. K. Mistry, R. Dawes, A. Choudhury, M. R. Van De Mark, J. Heterocycl. Chem. 51 (2014) 747.10.1002/jhet.1903Search in Google Scholar

28. J. Bats, Acta Crystallogr. B 32 (1976) 2866.10.1107/S0567740876009059Search in Google Scholar

29. A. D. Becke, Phys. Rev. A 38 (1988) 3098.10.1103/PhysRevA.38.3098Search in Google Scholar

30. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37 (1988) 785.10.1103/PhysRevB.37.785Search in Google Scholar

31. C. Møller, M. S. Plesset, Phys. Rev. 46 (1934) 618.10.1103/PhysRev.46.618Search in Google Scholar

32. J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, C. Fiolhais, Phys. Rev. B 46 (1992) 6671.10.1103/PhysRevB.46.6671Search in Google Scholar PubMed

33. J. P. Perdew, Y. Wang, Phys. Rev. B 45 (1992) 13244.10.1103/PhysRevB.45.13244Search in Google Scholar

34. J. P. Perdew, A. Ruzsinszky, G. I. Csonka, O. A. Vydrov, G. E. Scuseria, L. A. Constantin, X. Zhou, K. Burke, Phys. Rev. Lett. 100 (2008) 136406.10.1103/PhysRevLett.100.136406Search in Google Scholar PubMed

35. I. B. Obot, N. O. Obi-Egbedi, Colloids Surf. A 330 (2008) 207.10.1016/j.colsurfa.2008.07.058Search in Google Scholar

36. S. Benabid, T. Douadi, S. Issaadi, C. Penverne, S. Chafaa, Measurement 99 (2017) 53.10.1016/j.measurement.2016.12.022Search in Google Scholar

37. F. E.-T. Heakal, M. M. Osman, M. A. Deyab, A. E. Elkholy, Z. Phys. Chem. 232 (2017) 13.10.1515/zpch-2017-0949Search in Google Scholar

38. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr, J. E. Peralta, F. O. Ogliaro, M. J. Bearpark, J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N. J. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, D. N. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Gaussian, Inc., Wallingford, CT, USA, (2009).Search in Google Scholar

39. P. Pulay, Mol. Phys. 17 (1969) 197.10.1080/00268976900100941Search in Google Scholar

40. J. Clark Stewart, D. Segall Matthew, J. Pickard Chris, J. Hasnip Phil, I. J. Probert Matt, K. Refson, C. Payne Mike, Z. Kristallogr. Cryst. Mater. 220 (2005) 567.10.1524/zkri.220.5.567.65075Search in Google Scholar

41. D. R. Hamann, M. Schlüter, C. Chiang, Phys. Rev. Lett. 43 (1979) 1494.10.1103/PhysRevLett.43.1494Search in Google Scholar

42. B. G. Pfrommer, M. Côté, S. G. Louie, M. L. Cohen, J. Comput. Phys. 131 (1997) 233.10.1006/jcph.1996.5612Search in Google Scholar

43. K. Refson, P. R. Tulip, S. J. Clark, Phys. Rev. B 73 (2006) 155114.10.1103/PhysRevB.73.155114Search in Google Scholar

44. T. Koopmans, Physica 1 (1934) 104.10.1016/S0031-8914(34)90011-2Search in Google Scholar

45. R. G. Parr, L. V. Szentpály, S. Liu, J. Am. Chem. Soc. 121 (1999) 1922.10.1021/ja983494xSearch in Google Scholar

46. R. G. Pearson, Inorg. Chem. 27 (1988) 734.10.1021/ic00277a030Search in Google Scholar

47. Z. Zhang, N. Tian, X. Li, L. Zhang, L. Wu, Y. Huang, Appl. Surf. Sci. 357 (2015) 845.10.1016/j.apsusc.2015.09.092Search in Google Scholar

48. J. B. Foresman, A. Frisch, Æ. Frisch, Exploring Chemistry with Electronic Structure Methods, Gaussian Inc., Wallingford, USA (2015).Search in Google Scholar

49. C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edgington, P. McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van de Streek, P. A. Wood, J. Appl. Crystallogr. 41 (2008) 466.10.1107/S0021889807067908Search in Google Scholar

50. W. M. Haynes, CRC Handbook of Chemistry and Physics, 97th Edition, CRC Press, Boca Raton (2016).10.1201/9781315380476Search in Google Scholar

51. A. Bondi, J. Phys. Chem. 68 (1964) 441.10.1021/j100785a001Search in Google Scholar

52. J. E. Huheey, Inorganic Chemistry: Principles of Structure and Reactivity, Harper Collins College Publishers, New York, NY (1983).Search in Google Scholar

53. G. A. Guirgis, Y. D. Hsu, A. C. Vlaservich, H. D. Stidham, J. R. Durig, J. Mol. Struct. Theochem 378 (1996) 83.10.1016/S0166-1280(96)91003-9Search in Google Scholar

54. E. B. Wilson, J. C. Decius, P. C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra, Dover Publications, New York (2012).Search in Google Scholar

55. H. J. Schachtshneider, Vibrational Analysis of Polyatomic Molecules, Parts V and VI, Technical Report Nos. 231 and 57, Shell Development, Emeryville, California (1964/1965).Search in Google Scholar

56. D. Young, Computational Chemistry: A Practical Guide for Applying Techniques to Real World Problems, John Wiley & Sons, Inc., New York (2004).Search in Google Scholar

57. P. Pulay, G. Fogarasi, G. Pongor, J. E. Boggs, A. Vargha, J. Am. Chem. Soc. 105 (1983) 7037.10.1021/ja00362a005Search in Google Scholar

58. J. Baker, A. A. Jarzecki, P. Pulay, J. Phys. Chem. A 102 (1998) 1412.10.1021/jp980038mSearch in Google Scholar

59. M. S. Afifi, R. S. Farag, I. A. Shaaban, L. D. Wilson, W. M. Zoghaib, T. A. Mohamed, Spectrochim. Acta A Mol. Biomol. Spectrosc. 111 (2013) 277.10.1016/j.saa.2013.04.004Search in Google Scholar

60. I. A. Shaaban, A. E. Hassan, A. M. Abuelela, W. M. Zoghaieb, T. A. Mohamed, J. Mol. Struct. 1103 (2016) 70.10.1016/j.molstruc.2015.09.007Search in Google Scholar

61. Y. B. Shankar Rao, M. V. S. Prasad, N. Udaya Sri, V. Veeraiah, J. Mol. Struct. 1108 (2016) 567.10.1016/j.molstruc.2015.12.008Search in Google Scholar

62. S. Meng, Y. Zhao, J. Xue, X. Zheng, Spectrochim. Acta A Mol. Biomol. Spectrosc. 190 (2018) 478.10.1016/j.saa.2017.09.053Search in Google Scholar

63. N. B. Colthup, L. H. Daly, S. E. Wiberley, Introduction to Infrared and Raman Spectroscopy, Elsevier Science, Academic Press, New York (1990).Search in Google Scholar

64. P. Senet, Chem. Phys. Lett. 275 (1997) 527.10.1016/S0009-2614(97)00799-9Search in Google Scholar

65. D. K. Yadav, B. Maiti, M. A. Quraishi, Corros. Sci. 52 (2010) 3586.10.1016/j.corsci.2010.06.030Search in Google Scholar

66. S. Martinez, Mater. Chem. Phys. 77 (2003) 97.10.1016/S0254-0584(01)00569-7Search in Google Scholar

67. G. Gece, Corros. Sci. 50 (2008) 2981.10.1016/j.corsci.2008.08.043Search in Google Scholar

68. N. Khalil, Electrochim. Acta 48 (2003) 2635.10.1016/S0013-4686(03)00307-4Search in Google Scholar

69. M. S. Masoud, M. K. Awad, M. A. Shaker, M. M. T. El-Tahawy, Corros. Sci. 52 (2010) 2387.10.1016/j.corsci.2010.04.011Search in Google Scholar

70. F. Zhang, Y. Tang, Z. Cao, W. Jing, Z. Wu, Y. Chen, Corros. Sci. 61 (2012) 1.10.1016/j.corsci.2012.03.045Search in Google Scholar

71. A. Aloysius, R. Ramanathan, A. Christy, S. Baskaran, N. Antony, Egypt. J. Petrol. 27 (2018) 371.10.1016/j.ejpe.2017.06.003Search in Google Scholar

72. A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem. Phys. 83 (1985) 735.10.1063/1.449486Search in Google Scholar

73. B. Geboes, K. Baert, A. Hubin, T. Breugelmans, Electrochim. Acta 156 (2015) 308.10.1016/j.electacta.2015.01.036Search in Google Scholar

74. U. Ghani, N. Ullah, Bioorg. Med. Chem. 18 (2010) 4042.10.1016/j.bmc.2010.04.021Search in Google Scholar PubMed

Supplementary Material

The online version of this article offers supplementary material (DOI: https://doi.org/10.1515/zpch-2018-1346).

Received: 2018-11-25
Accepted: 2019-05-20
Published Online: 2019-06-22
Published in Print: 2020-03-26

©2020 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. The Effect of Crystalline Microstructure of PVDF Binder on Mechanical and Electrochemical Performance of Lithium-Ion Batteries Cathode
  3. Mechanistic Study on Surface Tension of Binary and Ternary Mixtures Containing Choline Chloride, Ethylene Glycol and Water (Components of Aqueous Solutions of a Deep Eutectic Solvent, Ethaline)
  4. Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations
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  6. Adsorption of 2,4-Dichlorophenoxyacetic Acid from Aqueous Solution Using Carbonized Chest Nut as Low Cost Adsorbent: Kinetic and Thermodynamic
  7. The Kinetics and Equilibrium Thermodynamics Study on the Removal of Direct Blue and Titan Yellow Dyes from Aqueous Media by Modified Rice Husk Char
  8. Investigation of Dielectric Properties, Electric Modulus and Conductivity of the Au/Zn-Doped PVA/n-4H-SiC (MPS) Structure Using Impedance Spectroscopy Method
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https://doi.org/10.1515/zpch-2018-1346
Keywords for this article
2,5-Dimercapto-1,3,4-thiadiazol (DMTD); tautomerism; Raman and infrared spectra; vibrational assignment and MP2 = full/DFT calculations

Articles in the same Issue

  1. Frontmatter
  2. The Effect of Crystalline Microstructure of PVDF Binder on Mechanical and Electrochemical Performance of Lithium-Ion Batteries Cathode
  3. Mechanistic Study on Surface Tension of Binary and Ternary Mixtures Containing Choline Chloride, Ethylene Glycol and Water (Components of Aqueous Solutions of a Deep Eutectic Solvent, Ethaline)
  4. Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations
  5. The Thermodynamic and pH Metric Binding Studies of Cu+2 Ions with Egg Protein by Spectrometric and Diffusion Current Techniques
  6. Adsorption of 2,4-Dichlorophenoxyacetic Acid from Aqueous Solution Using Carbonized Chest Nut as Low Cost Adsorbent: Kinetic and Thermodynamic
  7. The Kinetics and Equilibrium Thermodynamics Study on the Removal of Direct Blue and Titan Yellow Dyes from Aqueous Media by Modified Rice Husk Char
  8. Investigation of Dielectric Properties, Electric Modulus and Conductivity of the Au/Zn-Doped PVA/n-4H-SiC (MPS) Structure Using Impedance Spectroscopy Method
  9. Finding Solvent for Polyamide 11 Using a Computer Software
  10. Phytochemical Synthesis of Silver Nanoparticles Using Anthemis Nobilis Extract and Its Antibacterial Activity
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